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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Spinon excitations and spin correlations in the one-dimensional quantum magnet β -VOSO 4 probed by Raman spectroscopy

Fractionalized excitations such as spinons and anyons have emerged as a central theme in condensed matter physics with broad implications for superconductivity, quantum statistics, and quantum computation. The nearly ideal one-dimensional S = 1/2 system β-VOSO 4 without long-range order down to 85 mK provides a promising platform to experimentally explore such fractionalized excitations. Here, we employ Raman spectroscopy to probe magnetic excitations and the evolution of spin correlations in β-VOSO 4 . Spinon signatures are found along the chain direction, evidenced by a broad, gapless scattering continuum at low temperatures. The temperature dependence of the spinon spectral weight aligns considerably with numerical density matrix renormalization group calculations. By comparing the experimental spinon spectral weight with calculated results and evaluating the associated quantum Fisher information (QFI) therefrom, we observe a steep increase in QFI upon cooling, indicating rapidly growing correlation lengths. Our study showcases QFI as a probe of spin correlations in quantum magnets.

Wulferding, Dirk [Sejong Univ., Seoul (Korea, Repu↗
DOE OSTI2025

Relationship between microporous structure and light gas transport through glassy polymeric membranes revealed by molecular simulations

Microporous glassy polymers are attractive materials for gas separation membranes, due to their high permeability and tailorable selectivity, provided physical aging can be delayed. The archetypal microporous glassy polymer, PTMSP, can be blended with a hyper-crosslinked isatin–triptycene porous polymer network (PPN) to delay physical aging. However, while PPN is effective at reducing physical aging, it also affects the permeability of light gases through PTMSP. Molecular dynamics simulations were used here to shed fundamental light on the mechanisms responsible for these effects. Atomistic models are developed that satisfactorily reproduce experimental observations such as matrix density and cavity size distributions for neat PTMSP as well as for PTMSP–PPN blends. Analysis of the simulation results suggests that physical aging is delayed because the PPN inclusions slow down PTMSP relaxation while reducing the connectivity between free volume pockets. To understand how PPN inclusions affect light gas permeability, the atomistic models developed are used to probe CO 2 and CH 4 diffusion and sorption. These simulations are conducted for PTMSP matrices exhibiting varying density, towards reproducing experimental permeability data. Interrogating the simulation trajectories, it is discovered that while CH 4 travels preferentially through the free volume cavities, CO 2 preferentially interacts with the available surfaces, especially in the presence of PPN. These differences help interpret experimental observations. The transport of C 2 H 6 and H 2 S through PTMSP matrices was also investigated. These gases, and in particular H 2 S, were found to absorb within PTMSP, yielding very low diffusion coefficients. The ability to predict differences in diffusion pathways for various natural gas components unveils the possibility of engineering membranes to control permeability and selectivity towards large-scale applications.

Bao Le, Tran Thi [Univ. of Oklahoma, Norman, OK (U↗
DOE OSTI2024

Influence of globally spin-aligned vector mesons to the measurements of the chiral magnetic effect in heavy-ion collisions

The chiral magnetic effect (CME) in high-energy heavy-ion collisions arises from the interplay between the chirality imbalance and the intense magnetic field and will cause a charge separation along the magnetic field direction. While the CME search is still ongoing in experiments, the non-CME contributions need to be excluded from the CME observables. In this work, we examine the influence of globally spin-aligned ρ mesons on the γ 112 correlator, the R Ψ 2 (ΔS) correlator, and the signed balance functions, via a toy model and a multiphase transport model (AMPT). We find that the CME observables are sensitive to the 00-component of the spin density matrix, ρ 00 : they receive positive (negative) contributions when ρ 00 is larger (smaller) than 1/3.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Toward DMRG-tailored coupled cluster method in the 4c-relativistic domain

There are three essential problems in computational relativistic chemistry: Electrons moving at relativistic speeds, close lying states, and dynamical correlation. Currently available quantum-chemical methods are capable of solving systems with one or two of these issues. However, there is a significant class of molecules in which all the three effects are present. These are the heavier transition metal compounds, lanthanides, and actinides with open d or f shells. For such systems, sufficiently accurate numerical methods are not available, which hinders the application of theoretical chemistry in this field. In this paper, we combine two numerical methods in order to address this challenging class of molecules. These are the relativistic versions of coupled cluster methods and the density matrix renormalization group (DMRG) method. To the best of our knowledge, this is the first relativistic implementation of the coupled cluster method externally corrected by DMRG. The method brings a significant reduction of computational costs as we demonstrate on the system of TlH, AsH, and SbH.

Brandejs, Jan (ORCID:0000000221073095)↗
DOE OSTI2021

Two-color, intracavity pump–probe, cavity ringdown spectroscopy

Here, we report a proof-of-principle demonstration of intracavity pump–probe, cavity ringdown (CRD) detection in a three-mirror, traveling-wave cavity. With cavity-enhanced pump power and probe absorption path length, the technique is a generally applicable, high-sensitivity, high-selectivity detection method. In our experiments, the pump radiation is switched off during every other probe ringdown, which allows uncorrelated measurements of analyte and background cavity decay rates. The net, two-color signal from the difference between the pump-on and pump-off decay rates is immune to empty-CRD drifts and spectral overlaps from non-target molecular transitions. The immunity to the ringdown drifts allows longer signal-averaging and, thus, higher detection sensitivity. The ability to compensate for the background absorption enhances the detection selectivity in spectrally congested regions. Our technique is well-suited for trace-detection in the mid-IR region, where pump–probe schemes based on strong rovibrational transitions can be applied. In this work, two-color CRD detection is implemented on a ladder-type, three-level system based on the N 2 O, ν 3 = 1 ← 0, P(19) (pump) and ν 3 = 2 ← 1, R(18) (probe), rovibrational transitions. By frequency-locking two-quantum cascade lasers to the p-polarization (pump, Finesse = 5280) and s-polarization (probe, Finesse = 67 700) cavity modes, we achieve high intracavity pump power (36 W) and high probe ringdown rates (>2 kHz). The observed two-color spectra are simulated by a density-matrix, three-level system model that is solved under the constraints of the cavity resonance conditions. In addition to its background compensation capability, experimental flexibility in the selection of pump–probe schemes and signal insensitivity to intracavity laser power are further features that enhance the utility of our technique for mid-IR trace-detection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A graphene edge-mediated quantum gate

We propose a quantum gate architecture that allows for the systematic control of the effective exchange interactions between magnetic impurities embedded in nanoscale graphene flakes connected by a gated bridge. The entanglement between the magnetic moment and the edge states of the fragments is used to electrostatically tune the exchange interaction from ferro to antiferromagnetic by merely changing the bridge's carrier density. By characterizing the effects of size and coupling parameters, we explore different operation regimes of this device by means of exact calculations with the density matrix renormalization group. We analyze the results utilizing a simplified model that accounts for the main many-body mechanisms. Finally, we discuss how to use arrays of these devices to build quantum simulators for quantum many-body Hamiltonians.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Iterative subspace algorithms for finite-temperature solution of Dyson equation

One-particle Green’s functions obtained from the self-consistent solution of the Dyson equation can be employed in the evaluation of spectroscopic and thermodynamic properties for both molecules and solids. However, typical acceleration techniques used in the traditional quantum chemistry self-consistent algorithms cannot be easily deployed for the Green’s function methods because of a non-convex grand potential functional and a non-idempotent density matrix. Moreover, the optimization problem can become more challenging due to the inclusion of correlation effects, changing chemical potential, and fluctuations of the number of particles. In this paper, we study acceleration techniques to target the self-consistent solution of the Dyson equation directly. We use the direct inversion in the iterative subspace (DIIS), the least-squared commutator in the iterative subspace (LCIIS), and the Krylov space accelerated inexact Newton method (KAIN). We observe that the definition of the residual has a significant impact on the convergence of the iterative procedure. Based on the Dyson equation, we generalize the concept of the commutator residual used in DIIS and LCIIS and compare it with the difference residual used in DIIS and KAIN. The commutator residuals outperform the difference residuals for all considered molecular and solid systems within both GW and GF2. For a number of bond-breaking problems, we found that an easily obtained high-temperature solution with effectively suppressed correlations is a very effective starting point for reaching convergence of the problematic low-temperature solutions through a sequential reduction of temperature during calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Efficient evaluation of the Breit operator in the Pauli spinor basis

The frequency-independent Coulomb–Breit operator gives rise to the most accurate treatment of two-electron interaction in the non-quantum-electrodynamics regime. The Breit interaction in the Coulomb gauge consists of magnetic and gauge contributions. The high computational cost of the gauge term limits the application of the Breit interaction in relativistic molecular calculations. In this work, we apply the Pauli component integral–density matrix contraction scheme for gauge interaction with a maximum spin- and component separation scheme. We also present two different computational algorithms for evaluating gauge integrals. One is the generalized Obara–Saika algorithm, where the Laplace transformation is used to transform the gauge operator into Gaussian functions and the Obara–Saika recursion is used for reducing the angular momentum. The other algorithm is the second derivative of Coulomb interaction evaluated with Rys-quadrature. This work improves the efficiency of performing Dirac–Hartree–Fock with the variational treatment of Breit interaction for molecular systems. In conclusion, we use this formalism to examine relativistic trends in the Periodic Table and analyze the relativistic two-electron interaction contributions in heavy-element complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular dipole moment learning via rotationally equivariant derivative kernels in molecular-orbital-based machine learning

This study extends the accurate and transferable molecular-orbital-based machine learning (MOB-ML) approach to modeling the contribution of electron correlation to dipole moments at the cost of Hartree–Fock computations. A MOB pairwise decomposition of the correlation part of the dipole moment is applied, and these pair dipole moments could be further regressed as a universal function of MOs. The dipole MOB features consist of the energy MOB features and their responses to electric fields. An interpretable and rotationally equivariant derivative kernel for Gaussian process regression (GPR) is introduced to learn the dipole moment more efficiently. The proposed problem setup, feature design, and ML algorithm are shown to provide highly accurate models for both dipole moments and energies on water and 14 small molecules. To demonstrate the ability of MOB-ML to function as generalized density-matrix functionals for molecular dipole moments and energies of organic molecules, we further apply the proposed MOB-ML approach to train and test the molecules from the QM9 dataset. The application of local scalable GPR with Gaussian mixture model unsupervised clustering GPR scales up MOB-ML to a large-data regime while retaining the prediction accuracy. In addition, compared with the literature results, MOB-ML provides the best test mean absolute errors of 4.21 mD and 0.045 kcal/mol for dipole moment and energy models, respectively, when training on 110 000 QM9 molecules. The excellent transferability of the resulting QM9 models is also illustrated by the accurate predictions for four different series of peptides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Quantification of electron correlation for approximate quantum calculations

State-of-the-art many-body wave function techniques rely on heuristics to achieve high accuracy at an attainable computational cost to solve the many-body Schrödinger equation. By far, the most common property used to assess accuracy has been the total energy; however, total energies do not give a complete picture of electron correlation. In this work, we assess the von Neumann entropy of the one-particle reduced density matrix (1-RDM) to compare selected configuration interaction (CI), coupled cluster, variational Monte Carlo, and fixed-node diffusion Monte Carlo for benchmark hydrogen chains. A new algorithm, the circle reject method, is presented, which improves the efficiency of evaluating the von Neumann entropy using quantum Monte Carlo by several orders of magnitude. The von Neumann entropy of the 1-RDM and the eigenvalues of the 1-RDM are shown to distinguish between the dynamic correlation introduced by the Jastrow and the static correlation introduced by determinants with large weights, confirming some of the lore in the field concerning the difference between the selected CI and Slater–Jastrow wave functions.

Chemistry↗
DOE OSTI2022

Magnetic phases of spatially modulated spin-1 chains in Rydberg excitons: Classical and quantum simulations

Here, in this work, we study the magnetic phases of a spatially modulated chain of spin-1 Rydberg excitons. Using the Density Matrix Renormalization Group (DMRG) technique, we study various magnetic and topologically nontrivial phases using both single-particle properties, such as local magnetization and quantum entropy, and many-body ones, such as pair-wise Néel and long-range string correlations. In particular, we investigate the emergence and robustness of the Haldane phase, a topological phase of anti-ferromagnetic spin-1 chains. Furthermore, we devise a hybrid quantum algorithm employing restricted Boltzmann machine to simulate the ground state of such a system that shows very good agreement with the results of exact diagonalization and DMRG.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Two-color polarization spectroscopy measurements of Zeeman state-to-state collision induced transitions of nitric oxide in binary gas mixtures

We investigated collision induced transitions in the (0, 0) band of the A2Σ+–X2Π electronic transition of nitric oxide (NO) using two-color polarization spectroscopy (TCPS). Two sets of TCPS spectra for 1% NO, diluted in different buffer gases at 295 K and 1 atm, were obtained with the pump beam tuned to the R11(11.5) and OP12(1.5) transitions. The buffer gases were He, Ar, and N2. The probe was scanned while the pump beam was tuned to the line center. Theoretical TCPS spectra, calculated by solving the density matrix formulation of the time-dependent Schrödinger wave equation, were compared with the experimental spectra. A collision model based on the modified exponential-gap law was used to model the rotational level-to-rotational level collision dynamics. A model for collisional transfer from an initial to a final Zeeman state was developed based on the difference in cosine of the rotational quantum number J projection angle with the z-axis for the two Zeeman states. Rotational energy transfer rates and Zeeman state collisional dynamics were varied to obtain good agreement between theory and experiment for the two different TCPS pump transitions and for the three different buffer gases. One key finding, in agreement with quasi-classical trajectory calculations, is that the spin-rotation changing transition rate in the A2Σ+ level of NO is almost zero for rotational quantum numbers ≥8. It was necessary to set this rate to near zero to obtain agreement with the TCPS spectra.

Chemistry↗
DOE OSTI2023

Generalized spin σ -SCF method

We introduce a generalization of the σ-SCF method to approximate noncollinear spin ground and excited single-reference electronic states by minimizing the Hamiltonian variance. The new method is based on the σ-SCF method, originally proposed by Ye et al. [J. Chem. Phys. 147, 214104 (2017)], and provides a prescription to determine ground and excited noncollinear spin states on an equal footing. Our implementation was carried out utilizing an initial simulated annealing stage followed by a mean-field iterative self-consistent approach to simplify the cumbersome search introduced by generalizing the spin degrees of freedom. The simulated annealing stage ensures a broad exploration of the Hilbert space spanned by the generalized spin single-reference states with random complex element-wise rotations of the generalized density matrix elements in the simulated annealing stage. The mean-field iterative self-consistent stage employs an effective Fockian derived from the variance, which is utilized to converge tightly to the solutions. This process helps us to easily find complex spin structures, avoiding manipulating the initial guess. As proof-of-concept tests, we present results for Hn (n = 3–7) planar rings and polyhedral clusters with geometrical spin frustration. We show that most of these systems have noncollinear spin excited states that can be interpreted in terms of geometric spin frustration. These states are not directly targeted by energy minimization methods, which are meant to converge to the ground state. This stresses the capability of the σ-SCF methodology to find approximate noncollinear spin structures as mean-field excited states.

Chemistry↗
DOE OSTI2024

Noise reduction of stochastic density functional theory for metals

Density Functional Theory (DFT) has become a cornerstone in the modeling of metals. However, accurately simulating metals, particularly under extreme conditions, presents two significant challenges. First, simulating complex metallic systems at low electron temperatures is difficult due to their highly delocalized density matrix. Second, modeling metallic warm-dense materials at very high electron temperatures is challenging because it requires the computation of a large number of partially occupied orbitals. This study demonstrates that both challenges can be effectively addressed using the latest advances in linear-scaling stochastic DFT methodologies. Despite the inherent introduction of noise into all computed properties by stochastic DFT, this research evaluates the efficacy of various noise reduction techniques under different thermal conditions. Our observations indicate that the effectiveness of noise reduction strategies varies significantly with the electron temperature. Furthermore, we provide evidence that the computational cost of stochastic DFT methods scales linearly with system size for metal systems, regardless of the electron temperature regime.

Chemistry↗
DOE OSTI2024

Efficient simulation of open quantum systems coupled to a reservoir through multiple channels

It is challenging to simulate open quantum systems that are connected to a reservoir through multiple channels. For example, vibrations may induce fluctuations in both energy gaps and electronic couplings, which represent two independent channels of system–bath couplings. Systems of this kind are ubiquitous in the processes of excited state radiationless decay. Combined with density matrix renormalization group (DMRG) and matrix product states (MPS) methods, we develop an interaction-picture chain mapping strategy for vibrational reservoirs to simulate the dynamics of these open systems, resulting in time-dependent spatially local system–bath couplings in the chain-mapped Hamiltonian. This transformation causes the entanglement generated by the system–bath interactions to be restricted within a narrow frequency window of vibrational modes, enabling efficient DMRG/MPS dynamical simulations. We demonstrate the utility of this approach by simulating singlet fission dynamics using a generalized spin-boson Hamiltonian with both diagonal and off-diagonal system–bath couplings. This approach generalizes an earlier interaction-picture chain mapping scheme, allowing for efficient and exact simulation of systems with multi-channel system–bath couplings using matrix product states, which may further our understanding of nonlocal exciton–phonon couplings in exciton transport and the non-Condon effect in energy and electron transfer.

Chemistry↗
DOE OSTI2024

Thermal quasiparticle theory

The widely used thermal Hartree–Fock (HF) theory is generalized to include the effect of electron correlation while maintaining its quasi-independent-particle framework. An electron-correlated internal energy (or grand potential) is postulated in consultation with the second-order finite-temperature many-body perturbation theory (MBPT), which then dictates the corresponding thermal orbital (quasiparticle) energies in such a way that all fundamental thermodynamic relations are obeyed. The associated density matrix is of a one-electron type, whose diagonal elements take the form of the Fermi–Dirac distribution functions, when the grand potential is minimized. The formulas for the entropy and chemical potential are unchanged from those of Fermi–Dirac or thermal HF theory. The theory thus stipulates a finite-temperature extension of the second-order Dyson self-energy of one-particle many-body Green’s function theory and can be viewed as a second-order, diagonal, frequency-independent, thermal inverse Dyson equation. At low temperatures, the theory approaches finite-temperature MBPT of the same order, but it may outperform the latter at intermediate temperatures by including additional electron-correlation effects through orbital energies. Here, a physical meaning of these thermal orbital energies is proposed (encompassing that of thermal HF orbital energies, which has been elusive) as a finite-temperature version of Janak’s theorem.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Bootstrap embedding for interacting electrons in phonon coherent-state mean field

Here, we develop a Fermi–Bose bootstrap embedding framework for the ground state of interacting electrons coupled to a phonon mean field. The method combines bootstrap embedding for correlated electrons with a self-consistent coherent-state mean-field treatment for phonons. This method models the interacting electron–phonon problem as a system of correlated electrons traveling in a self-consistently specified potential landscape, allowing for efficient treatment of large lattice systems. Convergence of the methods for fragment size and total system size is demonstrated for the one-dimensional Hubbard–Holstein model for up to 350 sites. Finite-size scaling is performed to extrapolate to the infinite system size. Benchmarking against the density matrix renormalization group for a small 8-site system at half- and quarter-filling shows an orders-of-magnitude runtime advantage. The comparison further reveals that the method performs best in regimes dominated by localization, such as the Mott insulating phase and the strong-coupling tiny polaron regime, where the local embedding ansatz is still valid. However, due to the mean-field treatment for phonons, we find limitations of our methods in the weakly coupled delocalized region and at the Peierls transition, where quantum phonon fluctuations and long-range kinetic correlations become substantial.

Islam, Shariful [North Carolina State University, ↗